Polymers from hydrazine and tricarboxylic acid anhydrides

ABSTRACT

Novel polymers formed from the reaction of tricarboxylic anhydrides and hydrazines or hydrazides which may be crosslinkable by further reaction with a hydrazine or hydrazide are disclosed.

United States Patent Schimmel et al.

May 6, 1975 POLYMERS FROM HYDRAZINE AND TRICARBOXYLIC ACID ANHYDRIDESInventors: Karl F. Schimmel, Verona; Marco Wismer, Gibsonia. both of Pa.

Assignee: PPG Industries, Inc., Pittsburgh, Pa.

Filed: June 13, 1973 Appl. No.: 369,629

us. (:1 260/65; 117/124 E; 117/1284; 117/132 B; H7/l38.8 N; 117/141;117/148; 117/155; 117/161 P; 161/227; 260/252 N; 260/37 N; 260/47 CP;260/78 TF 1m. (:1. C08g 20/32 Field 61 Search 260/47 cP. 65, 38 TFReferences Cited UNITED STATES PATENTS 12/1967 Loncrini 260/78 FOREIGNPATENTS OR APPLICATIONS 45-37688 5/1970 Japan 260/78 OTHER PUBLICATIONSChem. AbsL, 688l6w, Korshak et 31., Vol. 70. 1969.

Primary Examiner-Lester L. Lee Attorney, Agent, or FirmRoberl DeMajistre4 Claims, No Drawings OL FROM HYDRAZINE AND dine functional is meant anyaliphatic radical having a TRICARBOXYUC ACID ANHYDRIDES chlorine,bromine or iodine atom or atoms and includes aromatics having aliphaticgroups containing chlorine, DESCRIPTION OF INVENTION bromine, or iodineatoms thereon connected to the aro- Briefly this invention comprisesnovel polymers pref- 5 gi i y formed from the reaction of a "icafboxylicIn the above formulae R is a trivalent organic radical hydride andmonofunctional alcohol form an esler having at least 2 carbon atoms.Examples of trivalent acid of the formula: organic radicals are, but notlimited to the aromatic trivalent radicals of the structure: l0

COR

HOC R l5 0 (IIIOH O CH I 3 l c 5 l ll CH3 do which is subsequentlyreacted with a hydrazine or hydrazide to form a polysalt having thestructural formula:

O O 0 O u n 9 o u u o R OC CO H N N C R C N NH 3 I y 1 y l x 3 R R R COe the above polysalt is then heated to form a compound 50 and the like,and the aliphatic and cycloaliphatic trivaof the structural formula:lent organic radicals, such as (III) ti l M l i \i N--L- R N N -C R C t:l 1 W Y X H C R2 R3 the above (lll), when R is aldehyde ketone,aliphatic 65 chlorine, bromine or iodine functional, can be further 5reacted with a hydrazine or hydrazide to form a crosslinked network. Byaliphatic chlorine, bromine or io- Cminued R is a monovalent alkylcycloalkyl or alkenyl radical having 1 to 20 carbon atoms R and R areselected from the group consisting of monovalent alkyl, aryl, aralkyl,cycloalkyl, heterocy- 5 cloalkyl and hydrogeno radicals and isomersthereof,

and x and y are either 0 or 1. I Any hydrazine or dihydrazide issuitable for crosslinking the compounds of formula III (when R isketone, aldehyde, aliphatic chlorine, bromine or iodine I containing),provided the hydrazine or dihydrazide has two terminal Nl-l groups,examples of hydrazines useful for cross-linking are, but not limited to;hydrazine,

and the like. R is a divalent organic having at least 2 1,2-ethylenedihydrazine, p-phenylene dihydrazine, alcarbon atoms; examples of saiddivalent organic radipha, alpha'-diethyl-m-phenylene dihydrazine, andthe cals are, but not limited to, the aromatic divalent orlike; examplesof hydrazides are, but not limited to, ganic radicals, such as:succinoyl dihydrazide, adipoyl dihydrazide, isophthal- C1 Cl Br Br Q Q IQ C1 C1 52 BI.

CH2 C";-

I I i N and the like, and the divalent organic aliphatic radicals, oyldihydrazide, terephthaloyl dihydrazide, pyridine- Such 2,4-dicarbonyldihydrazide and the like.

The cross-linking reaction is accomplished, when R +CH2+" is aldehyde orketone functional, by reacting the carrii n is 2 l0 bonyl containingpolymer with the hydrazine or hydra- C C -i:ci:c-c-c clc L C ccll c c ccand the like. zide to form a cross-linking bridge of the structurewherein R R R x and y are of the structures and vaiues as previouslydescribed.

The cross-linking reaction is effected by the ketone or aldehydecarbonyl reacting, i.e., condensing, with the terminal Nl-l group of thehydrazine or hydrazide employed to produce the cross-linked polymer andthe water of condensation as a by-product. When the functionality of Ris aliphatic chlorine, bromine or iodine, the terminal NH; groups of thehydrazine of hydrazide react with the halogen bearing carbon atom toproduce a cross-linking bridge of the structural formula (it (ii i l I y1 I y wherein R,, R R x and y are of the structures and values aspreviously described.

Hence, the physical properties of the final polymeric material can beadjusted by the degree of cross-linking of the polymer. Further, thedegree of cross-linking can be varied by the amount of ketone, aldehyde,aliphatic chlorine, bromine or iodine functional tricarboxylic anhydrideused in the synthesis of the polymer. The degree of cross-linking canalso be varied by the stoichiometric amount of the hydrazine or thehydrazide used in the synthesis of the polymer. Therefore, a wide rangeof chemical and physical properties of the cross-linked polymer can beachieved, making the cross-linked polymers of the instant inventionadaptable for a plurality of uses.

The polymers of the instant invention can be further modified bysubstituting a portion of the hydrazine or dihydrazide in formula IIwith a diamine, thereby introducing polyimide groups into the polymerchain. Suit- N l a groups along the polymer cahin. These tetracarboxylichydrazine or hydrazide reaction products being more fully described incopending application Ser. No. 369,628, filed concurrently herewith.

The preferred method of forming the polymers of the instant inventioncomprises: admixing 1 mole of tricarboxylic dianhydride with a suitablesolvent, adding 1 mole of monofunctional alcohol to form the acid esterof formula I, subsequently adding the hydrazine or dihydrazide (in asufficient amount to form either the cross-linked or noncross-linkedpolymer on heating) to produce the polysalt of formula II. At this stagethe solution can be further reduced in polyslat concentration by theaddition of an aqueous nitrogenous base solution consisting of aqueousammonia or amine solution or additional organic solvent. The polysalt,either aqueous or non-aqueous, can be coated on a substrate such asglass, glass fibers, metal, wood or the like and heated to a temperatureof about 200C. to form either the compound of formula III or thecross-linked version thereof.

Another method of forming the polymers of the instant inventioncomprises admixing 1 mole of the tricarboxylic dianhydride with themonofunctional alcohol to form the ester diacid of the tricarboxylicacid, and subsequently adding the hydrazine or dihydrazide (in an amountsufficient to form either the cross-linked or noncross-linked polymer onheating) and subsequently heating the mixture to above 100C. to form apolysalt having the structural formula:

0 0 0 0 c x 31 HOiI -R H 2 The above method has been characterized byspecific molar amounts of reactants, however different molar amounts maybe used providing the molar ratios of the reactants remain the same.

The latter method of forming the polymers of the instant invention isdesired in order that the hydrazine or hydrazide is chemically bonded tothe trifunctional R group, hence, eliminating the possibility ofvaporization of the hydrazine or hydrazide on subsequent heating causinga disproportionation of the stoiehiometry of the reactants.

Suitable solvents for admixing with the tricarboxylic anhydride arethose having a high degree of polarity. Examples of such solvents areN-N-dimethyl acetamide', N,N-dimethyl formamide; dimethyl sulfoxide;Nmethyl pyrrole, methyl isobutyl ketone, ethyl alcohol and the like.

Transesterification catalysts can be used to aid in the conversion ofthe polysalt to the polymer of formula II]. Examples of suchtransesterification catalysts are, but not limited to, oxalic acid,dimethyl terephthalate, dibutyl sebacate, butyl stannoic acid and thelike.

Coating techniques known to those skilled in the art can be used fordepositing the polysalts of formula 11 on the desired substrate. Forexample, when the compound of formula Ill is to be used a binder forglass fibers, application can be achieved by dipping a mat of glassfibers, or glass fiber paper into an aqueous ammonia polysalt (formula11) solution and allowing the glass fiber material to soak into saidglass fibers (approximately 1 to 30 seconds). After soaking, the glassfiber material is permitted to drip dry and then is subsequently bakedat approximately 250F. to 300F. for about 30 to (10 minutes. Thus, fiberglass paper or fiber glass mat is produced which may toleratetemperatures of up to greater than 500F. without substantial loss ofstrength or integrity.

The polymers of the instant invention can be used as binders for fiberssuch as cotton, hemp, wool, hair, silk. rayon, nylon, Orion, saran,Ardil, and the like in addition to glass fibers to impart temperatureresistance and strength to the aforementioned fibers.

Fiber reinforced laminates and castings and nonreinforced castings canbe produced by the polymers of the instant invention where certainchemical and physical properties are desired.

Further. coated metallic conductive wire such as copper or Zinc, can beproduced by dipping the selected wire into the polysalt (formula 11)solution, (the solution being aqueous or nonaqueous) and subsequentlyheating the polysalt coated wire to a temperature adequate to convertthe polysalt to the polymer of formula III or a cross-linked versionthereof. Wire coated by polymers having the repeating structural unit of(formula III) or the cross-linked version thereof may withstand servicetemperatures of 400F. without any observable degeneration of the polymercoating; thus, an insulated wire is produced capable of withstandingelevated service temperatures. The coating thickness on the surface ofthe wire can be adjusted by the viscosity of the polysalt solution. Alow centipoises at 20C.) viscosity polysalt solution would produce athin coating 10 microns) and a high viscosity 1000 centipoises at 20C.)polysalt solution would produce a thick coating (about microns).

Also. flat or contoured substrates such as the cellulosics includingwood, paper and the like; glass, metal and the like can be coated withthe polysalt of formula II by spraying the low viscosity polysaltsolution by conventional spraying techniques; by applying the polysaltsolution with a standard paint brush, by depositing the polysaltsolution by any other conventional coating techniques; the techniqueselected being contingent on the substrate and film thickness desired.

The polysalt can be pigmented with pigments such as titanium dioxide,zinc oxide, calcium carbonate, lithopone, phthalocynine blue, carbonblack, iron oxide or the like to impart color to the coating or withsilica, clay, talc and the like to impart the desired film and solutionproperties to the polysalt and subsequently formed polymer. The polysaltwhich is deposited on a substrate may be used as a coating in itself,due to the hard. cohesive properties of the polysalt after the solventand/or water and ammonia evaporate, or the poly salt can be heated toform the polymer of formula Ill or the cross-linked version thereof. lffire retardant coating properties are desired, the polysalt film itselfis the desired coating, however, the polymer of formula ill or thecross-linked version thereof also imparts fire retardantcharacteristics.

In addition, adhesive compositions can be formed by the polymers of theinstant invention in that the polymer structure can be adapted to havebonding characteristics to metal, glass. mica, asbestos, wood, paper andlike substrates.

The invention will be more clearly illustrated by the examples below;however, these examples which describe specific embodiments should notbe construed to limit the invention in any way.

EXAMPLE 1 Solution A To a two liter round bottom flask equipped with awater cooled reflux condenser, a thermometer, a heating mantle and amechanical agitator was charged 500 grams of trimellitic anhydride 1,2,4benzenetricarboxylic acid monoanhydride) and 500 grams of ethyl alcohol.The mixture was heated to reflux and refluxed for l hour and then cooledto room temperature. The mixture did not form a solution. 250 grams ofthe above mixture was placed in a five liter beaker and manuallyagitated at ambient temperature with 500 grams of water and 500 grams ofethyl alcohol until a clear solution was formed.

Solution B 52 grams of hydrazine hydrate was added to 350 grams of waterat ambient temperature and manually agitated until homogeneous.

Polysalt Formation and Binder Solution Solution B was added to SolutionA with manual agitation at ambient temperature and stirred untilhomogeneous. Subsequently, l 152 grams of water was added to the abovesolution at ambient temperature with agitation and a homogeneoussolution resulted.

Application to Glass Fiber Paper Glass fiber paper was dipped in thebinder solution for about 3 seconds and then the glass fiber paperpercent glass fibers) with the binder solution thereon was heated to300F. for 1 hour in a forced air oven. Microscopic examination of thecoated glass fiber paper showed a uniform coating of binder on the glassfibers. Two samples of glass fiber paper coated as abo e describedexhibited good strength and after 4 hours of subjecting the above coatedglass fiber paper samples to 600F., the polymer weight loss of eachsample was 16.41 percent i 0.61 percent.

EXAMPLE I] A binder solution was formed in accordance with thecomponents and procedure of Example I, but the additional 1152 grams ofwater was not added after the polysalt was formed,

This hinder solution was applied to the glass fiber paper (100 percentglass fibers) by supporting sand paper on a Buchner funnel having thesame interior Cllmensions and configuration as the glass fiber pape andpouring the binder solution onto the glass fiber paper while applying avacuum to the surface of the glass fiber paper opposite the surface ofinitial contact with the binder solution. Two samples of the glass fiberpaper coated as above described exhibited good strength and aftersubjecting the above coated glass fiber paper samples to 600F. for 4hours, the polymer weight loss of each sample was 1 1.64 percent 1 0.20percent.

EXAMPLE lll Preparation of Terephthaloyl Dihydrazide Solution A To a twoliter round bottom flask equipped with a water cooled reflux condenser,a thermometer, a heating mantle and a mechanical stirrer was charged 192grams of trimellitic anhydride and 350 grams of ethyl alcohol. Themixture was heated and refluxed for l hour and then cooled to roomtemperature. The mix ture formed a homogeneous solution.

Solution B 213 grams of terephthaloyl dihydrazide was mixed, employingmanual agitation, in a three liter beaker with 500 grams of pyrollidoneand 200 grams of water at ambient temperature until a homogeneoussolution was formed.

Polysalt Formation and Binder Solution Solution A was added to SolutionB with manual agitation at ambient temperature.

The above binder solution was coated on 100 percent glass fibers inaccordance with the procedure of Example ll. Two samples of the glassfibers coated as above described, exhibited good strength and aftersubjecting the above coated glass fiber paper samples to 600F. for 4hours, to polymer weight loss of each sample was about 50 percent.

EXAMPLE lV Solution A To a two liter round bottom flask equipped with awater cooled reflux condenser, a thermometer, a heating mantle and amechanical agitator is charged 192 grams of trimellitic anhydride and350 grams of ethyl alcohol. This mixture is heated to reflux for l hourand allowed to cool to room temperature.

Solution B 40 grams of 85 percent hydrazine hydrate is mixed usingmanual agitation, with 350 grams of water at ambient temperature in athree liter beaker.

Polysalt Formation Solution A is added to Solution B at ambienttemperature using manual agitation. A homogeneous solution was formed.

The above polysalt is coated on a cold rolled steel panel and allowed toair dry for 24 hours. A film produced in this manner is continuous, hardand demonstrated fire retardancy when exposed to open flame.

Although the present invention has been described with respect tospecific details of certain embodiments thereof, it is not intended thatsuch details act as limitations upon the scope of the invention exceptinsofar as is set forth in the accompanying claims.

We claim:

1. An organic condensation polymer consisting essentially of thereaction product of a benzenetricarboxylic monoanhydride and hydrazine,being further characterized by the repeating structural formula:

2. An organic condensation polymer consisting essentially of therepeating structural formula:

1. AN ORGANIC CONDENSATION POLYMER CONSISTING ESSENTIALLY OF THEREACTION PRODUCT OF A BENZENETRICARBOXYLIC MONOANHYDRIDE AND HYDRAZINE,BEING FURTHER CHARACTERIZED BY THE REPEATING STRUCTURAL FORMULA:
 2. Anorganic condensation polymer consisting essentially of the repeatingstructural formula:
 3. The polymer of claim 2 wherein R is ketonefunctional.
 4. The polymer of claim 3 wherein R has the structuralformula: